JPH0292957A - Thermoplastic resin composition improved in resistance to stress cracking and impact - Google Patents

Abstract

PURPOSE:To obtain the title composition by blending a polyphenylene ether resin, styrene resin and a premixed composition comprising a polyolefin resin and a specific resinous block copolymer. CONSTITUTION:The objective composition can be obtained by blending a total of 100 pts.wt. of (A) 20-80 pts.wt. of a polyphenylene ether resin [e.g., poly(2,6- dimethyl-1,4-phenylene)ether] and (B) 80-20 pts.wt. of a styrene resin (e.g., polystyrene, rubber-modified high-impact polystyrene) with (C) 1-20 pts.wt. of a premixed composition comprising C1: 30-70 pts.wt. of a polyolefin resin (e.g., polyethylene, polypropylene) and C2: 70-30 pts.wt. of a resinous block copolymer 100000-600000 in weight-average molecular weight of the formula (A is vinyl aromatic block; B is conjugated diene hydrocarbon of specified unsaturation degree; n is 1 or 2).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition with improved impact resistance and stress cranking resistance.

[Conventional technology and its problems]

Polyphenylene ether is a resin that has attracted much attention in recent years because of its excellent mechanical properties, electrical properties, and heat resistance, as well as its low water absorption and good dimensional stability. However, since polyphenylene ether resin alone generally has poor processability and impact strength, in many industrial applications it is used as a blend with polystyrene or rubber-reinforced polystyrene.

On the other hand, it is also a trend in recent years that the shapes of industrial parts and electrical parts are becoming more complex, and the properties of resins are also becoming more and more demanding.
In particular, in terms of impact resistance and stress crack resistance, the above-mentioned resins are no longer able to adequately meet these uses.

In order to meet these demands, some techniques have been proposed for adding polyolefin polymers. For example, Japanese Patent Publication No. 7069/1983 describes a resin composition consisting of a polyphenylene ether resin and a polyolefin polymer. However, the desired improvement effect is insufficient, and if the amount of polyolefin polymer is increased to obtain a sufficient effect, peeling occurs in the molded article, which is not preferable.

JP-A-56-71742 discloses (a) polyphenylene ether resin, (b) polystyrene resin, (c)
A resin composition composed of an A-B-A type hydrogenated block copolymer is disclosed, and the system does not contain a polyolefin polymer according to the text description and examples.

Furthermore, the block copolymer is the above-mentioned specific block copolymer, and the improvement effect is not sufficient. Also, Tokukai@53
Publication No. 71158 describes (a) a polyphenylene ether resin, (b) a polystyrene resin, (C) a pre-blended mixture of a polyolefin polymer and a hydrogenated block copolymer, and (d) a hydrogenated block copolymer. A resin composition consisting of a combination is described. However, the block copolymers used are specific elastomers. Furthermore, to achieve the desired effect, the addition of the preformulated mixture alone is not sufficient, as demonstrated in the control experiment (although the coexistence of the corresponding hydrogenated block copolymer is shown to be essential). In addition, JP-A-54-88960 discloses (a) polyphenylene ether It resin, (
A resin composition comprising b) an A-B-Affi block copolymer and (c) a polyolefin polymer is disclosed. According to the main text and examples, this invention is a system that does not contain a polystyrene resin, does not perform preliminary mixing of components (b) and (e), and has a block copolymer of (bl) with -f This is a specific A-B-All block copolymer that has elasticity.Also, the improvement effect is not sufficient.

In addition, in the example of Japanese Patent Application Laid-Open No. 61-223054,
(a) Ho! J Fue et al. Reno ether, (b) S f Reno M
(c) A block copolymer having A-B-A IJ and an A component content of 70 to 90% by weight, and (d) a resin composition consisting of various nidistomers.

Further, US Pat. No. 3,835.200 describes A-B-Afi and the content of the A component is 65 to 8.
A technique is disclosed in which 10 to 80% by weight of a block copolymer of 5% by weight is added. Additionally, U.S. Patent No. 4.32
No. 2,507 discloses a technique in which 10 to 90% by weight of an ABA hydrogenated block copolymer is added.

None of these inventions involve premixing, and in Sarabutton, the block copolymer is the above-mentioned specific block copolymer, and the improvement effect is insufficient.

Among the above-mentioned prior art compositions aimed at improving impact resistance, although the effect of improving impact resistance is recognized to some extent, they are not fully satisfactory depending on the intended use. In order to obtain a highly satisfactory effect of improving impact resistance, it is necessary to increase the amount of the polyolefin polymer and block copolymer as additives. This causes problems such as peeling of the molded product and deterioration of the appearance, rigidity, and heat resistance of the molded product, and is extremely undesirable from a practical standpoint.

Further, in the process of achieving the present invention, it was found that some of the above-mentioned stress crank resistance properties are also improved, but this is not enough to sufficiently solve practical problems.

[Means and effects for solving the problems] The object of the present invention is to provide a thermoplastic resin composition that has good impact resistance, stress crack resistance, and molded product appearance without reducing the excellent performance of polyphenylene ether resin. It is about providing something.

That is, the present invention comprises: (a) 20 to 80 parts by weight of polyphenylene ether resin;
and (b) 80 to 20 parts by weight of styrenic resin, total 1
00 parts by weight JC, ((ripolyolefin resin 30-70
Parts by weight and general formula AB+A-B Hydrocarbon block, n is an integer of 1 or 2, A
The present invention relates to a thermoplastic resin composition containing 1 to 20 parts by weight of a pre-crosstalk composition comprising 70 to 30 parts by weight of a resinous block copolymer (having a component content of 50 to 65% by weight).

The thermoplastic resin composition of the present invention is characterized in that it contains a premixed mixture of a polyolefin polymer and a resinous block copolymer represented by A-BAA-B). Therefore, when observing the morphology, it forms a characteristic structure. In other words, the polyolefin polymer and block copolymer added without premixing are mostly dispersed individually, whereas the resin composition of the present invention has a polyphenylene ether resin and a styrene resin. It is dispersed as fine particles with a volume average particle diameter of 0.05 to 0.5μ in a homogeneous resin matrix, and its microstructure has a two-layer structure in which a dispersed polyolefin resin is coated with a resinous block copolymer. ing. By forming this two-layer structure, the resin composition of the present invention dramatically improves the adhesion between the matrix phase of polyphenylene ether resin and styrene resin and the dispersed polyolefin polymer. Presumed. As a result, stress transmission between both phases is carried out smoothly, and the objectives of the present invention, such as significantly improving impact strength, improving stress cranking resistance, and preventing deterioration of the appearance of molded products due to the addition of different polymers, can be achieved. It is estimated that this will be effective. In order to exhibit such a microstructure and the effects of the present invention that are presumed to be based on this microstructure, a polyolefin polymer and a resinous block copolymer containing A-Bah-B are melt-preliminarily kneaded. While it is essential to do so, the selection of the block copolymer is also important.

From this point of view, the present invention provides a resinous block copolymer represented by A-BAA-B)n, in which the A component is a vinyl aromatic block, and the content thereof is from 50% by weight to 65% by weight.
% by weight, and the weight average molecular weight is 100.000
~600,000. Component B uses a specific resinous block copolymer which is a conjugated diene hydrocarbon block whose degree of unsaturation has been reduced to 10% or less of the initial degree of unsaturation by hydrogenation, and a polyolefin polymer. and the above resinous block copolymer in a ratio of 30 to 70:30 to 7.
This was achieved by setting K to 0 (parts by weight).

The polyphenylene ether resin used in the present invention has the formula (where Q, Q', Q'' and Q'' are hydrogen, halogen, hydrocarbon group, halohydrocarbon group, hydrocarbonoxy group,
and halohydrocarbonoxy groups, where n represents the total number of monomer units and is an integer of at least 80). Particularly preferred are poly(2,6-dimethyl-1,4-)unileno)ether and 2.3-dimethylphenol.
．． It is a copolymer of 6-drimethylphenol.

Specifically, the styrenic resin used in the present invention is:
General formula % Formula % (In the formula, R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen, and 2 is a one-membered group selected from the group consisting of a vinyl group, hydrogen, or an alkyl group having 1 to 4 carbon atoms. and p is 1 to 5) containing at least 50 mol% of polymer units derived from vinyl aromatic monomers.

Preferred styrenic resins are polystyrene, polychlorostyrene, α-methylstyrene homopolymer, and rubber-modified impact styrenic resins, such as polystyrene modified with natural or synthetic rubber. Further, styrene-containing copolymers such as styrene-acrylonitrile copolymer, styrene-acrylonitrile-α-methylstyrene copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-maleic anhydride copolymer, etc. .

In a total of 100 parts by weight with polyphenylene ether resin,
The styrene resin is used in an amount of 20 to 80 parts by weight. 20
If the amount is less than 80 parts by weight, the moldability will be markedly poor, and if it exceeds 80 parts by weight, the heat resistance of the final composition will deteriorate, which is not preferred.

The polyolefin polymer used in the present invention includes:
Examples include not only polyethylene, polypropylene, polyisobutylene, and copolymers of ethylene and propylene, but also copolymers of ethylene and organic esters such as ethylene vinyl acetate, ethylene ethyl acrylate, and ethylene methyl acrylate. Further, for example, these materials may be chemically modified with maleic anhydride, maleic acid, or the like. These are commercially available or can be made by known methods.

The general formula used in the present invention is A-B+h-B)n (where A is a vinyl aromatic hydrocarbon and B is a conjugated diene whose degree of unsaturation has been reduced to 10% or less of the initial degree of unsaturation by hydrogenation) The resinous block copolymer represented by hydrocarbon (n is an integer of 1 or 2, the content of component A is 50 to 65% by weight) has a Young's modulus of 13.000 J/cm or more. It is a rigid substance that is distinguished from a rubber-like elastic body, and the content of component A is more than 50% by weight and 65% by weight or less, preferably 55 to 65% by weight.
and a weight average molecular weight of 100.000 to 600,00
0, preferably 120.000 to 500.000. If the content of component A is less than 50% by weight, the gloss of the molded product will be poor (and if it is more than 65% by weight, the desired improvement effect will not be sufficient).If component B is not hydrogenated, the resinous block copolymer will It is unfavorable due to poor thermal stability.

Furthermore, if the amount of hydrogen added exceeds 10%, the desired improvement effect will not be sufficient.

The vinyl aromatic hydrocarbons mentioned above include styrene, 0-
Methylstyrene, p-methylstyrene, p-tert
-7'tylstyrene, l,3-dimethylstyrene, α
-Methylstyrene, vinylnaphthalene, vinylanthraceno, particularly styrene. These may be used not only alone but also as a mixture of two or more. Further, examples of conjugated diene hydrocarbons include diolefins having a pair of conjugated double bonds having 4 to 8 carbon atoms, such as 1,3-butadiene, 2-methyl 1,3-butadiene (isoprene), 2
．． Examples include 3-dimethyl 1,3-7'tadiene, 1,3-pentadiene, 1,3-hexadiene, and particularly common ones include 1,3-butadiene and isoprene. These may be used not only as a single type but also as a mixture of two or more types. These can be manufactured by known methods. For example, it can be produced using n-butyllithium as a catalyst in a cyclohexane solvent under a nitrogen atmosphere. Hydrogenation can also be carried out using solid hydrogenation catalysts, such as nickel supported on quartzite and fine precious metals supported on low surface area catalysts.

The ratio of the pre-crosstalk composition of the polyolefin polymer and the resinous block copolymer represented by A-B÷A-B)n is 30 to 70 nia 0 to aO (parts by weight), preferably 35 to
65: 65 to 35 (parts by weight). When the polyolefin resin exceeds 70 parts by weight, peeling is likely to be observed on the fractured surface even in molded articles made of the resin composition of the present invention, while when it is less than 30 parts by weight, the resin composition
The desired improvement effect is lacking.

The preliminary crosstalk composition is 1 part by weight per 100 parts by weight of (a) polyphenylene ether resin and (b) styrene resin.
~20 parts by weight is used. If the amount used is less than 1 part by weight, little improvement effect will be seen, and if it exceeds 20 parts by weight, properties such as rigidity and good heat resistance that polyphenylene ether systems originally have will be impaired, which is not preferable.

The method for producing the premixing composition in the present invention includes extruders, kneaders, etc. commonly used for kneading resins, and melt mixing methods such as roll mixers and Banbury mixers commonly used for rubber mixing processing. used.

Depending on the purpose, the resin composition of the present invention may contain conventionally known additives such as phosphoric acid esters, melamine flame retardants, etc.
Flame retardants such as 0-gun flame retardants, red phosphorus, polybutene, low molecular weight polyethylene, mineral oil, epoxidized soybean oil, polyethylene glycol, plasticizers such as fatty acid esters, phosphite esters, hindered phenols, alkano - Stabilizers such as ruatane, acid amides, dithiocarbamate metal salts, inorganic sulfides, metal oxides, mild ultraviolet absorbers, colorants, mold release agents, etc. may be added. can.

The resin composition of the present invention also includes reinforcing fillers such as glass fiber, glass break, mica, carbon fiber, various metal fibers, various metal breaks, asbestos, wollastonite, calcium carbonate, talc, mica, zinc oxide,
By blending potassium titanate, titanium oxide, glass beads, etc., a filler-containing resin composition having even higher rigidity and heat resistance can be obtained.

If a conductive filler such as carbon fiber is selected as the filler, functions such as conductivity and electromagnetic shielding properties can be imparted.
The composition of the present invention is no exception.

The resin composition of the present invention includes (a), (b), (cl
and other components extruder, kneader roll mixer
It is obtained by melt-mixing using a Banbury mixer or the like. Preferred is an extruder.

The resin composition of the present invention obtained by 5K can be molded into sheets, foams, films, and injection molded products of various shapes by any conventionally known molding method, such as extrusion molding, injection molding, and blow molding. It can be easily molded into a wide variety of practically useful products such as blow molded products, pressure molded products, and vacuum molded products.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited to the following examples. In addition, in the examples, parts indicate parts by weight. In addition, physical property values were measured by the following method.

Heat resistance: Using an injection molded test piece with a thickness of y4#, JIS
- The heat deformation temperature (hereinafter abbreviated as H, D, T) was measured at 4- with a load of 18.6 according to 7207.

Impact strength: Using an injection molded test piece with a thickness of Z', AST
Notched Izot impact strength was measured according to M-D-638 (measurement temperature 23°C).

Flexural modulus: ASTM-D-790 Stress crack resistance: Using a compression molding machine, the resin composition was molded at 250°C to a thickness of 31 m+ and a width of 12.7 mm.
, a test piece sample with a length of 120B is prepared. This test piece was kneaded at 80° C. for 24 hours in a hot air dryer for 7 times to remove residual strain. Next, one end of this test piece was held in a creep rupture measuring machine manufactured by Seiwa Riko, a load of 1 o'clock was set on the other end, and shaft grease D (manufactured by Sahara Tokushu Oil Co., Ltd.) was applied at a position 20 o'clock from the load setting side. After applying .29, it is kept in a constant temperature room at 23° C. and 50% humidity, and the time until breakage is measured. The longer the time until breakage, the better the stress crack resistance.

Peelability: An injection molded test piece with a thickness of 3' was used and its fracture surface was observed.

Evaluation rank ○: No peeling at all Δ; Slight peeling ×: Particularly severe peeling Appearance: Color the gloss on the gate side of a 2" thick injection molded test piece Computer SM 30H (manufactured by Suga Test Instruments C Co., Ltd.)
It was measured with

The degree of gloss was expressed numerically. The larger the number, the better the gloss.

Furthermore, the raw materials used in the Examples and Comparative Examples are as shown in Table 1, but are far below.

Polyphenylene ether; ηmp/c = o, s
Poly(2,6
-dimethylphenylene-1,4-ether). (Hereafter P
(abbreviated as PE) Styron QH405; manufactured by Asahi Kasei Industries, Ltd., high impact polystyrene Stylon 685; manufactured by Asahi Kasei Industries, Ltd. (Ten), polystyrene polyethylene M-1703; manufactured by Asahi Kasei Industries, Ltd., low density polyethylene (MFRo, 3. Density 0.917
) Polyethylene M-6520; Manufactured by Asahi Kasei Kogyo (Ten), low density polyethylene (MFR2G, density 0.91
5) Polyethylene F-2270; Asahi Kasei Qv
made of low-density polyethylene (MFR7, O, density 0.92
2) Polyethylene LM-2408S; Asahi Kasei Kogyo (
(MFRo), linear low-density polyethylene (MFRo, 8.
Density 0.924) JSRFP07P; Manufactured by Japan Synthetic Rubber Co., Ltd., ethylene-
Propylene terpolymer (EPDM) (Mooney viscosity 7
0. Specific gravity 0.86) Toughprene A; Asahi Kasei Kogyo (a)
A-B-A-B disc styreno-butadiene block copolymer (styrene content: 40% by weight) manufactured by A-B-A-B Co., Ltd. [Production of block copolymer] The monomers in Part A1 were polymerized at about 70° C. according to the monomer amounts shown in Table 1, and after the monomers were substantially completely polymerized, 83 parts of monomers were added and polymerized. After the added monomers have substantially completely polymerized, parts A, #B, and so on are sequentially added in the same manner! A linear block copolymer was obtained by combining them.

Each block copolymer obtained contains 2,4 as a stabilizer.
-D-tart-butyl-p-cresol, trisnonylphenyl phosphite and phenothiazine were each added in an amount of 0.5 parts by weight per 100 parts by weight of the block copolymer.

Hydrogenation can be carried out using a variety of hydrogenation catalysts, such as nickel supported on diatomaceous earth, Raney nickel, copper chromate, molybdenum sulfide, and finely divided platinum or other noble metals supported on low surface area catalysts.

Hydrogenation may be carried out at any desired temperature or pressure, such as atmospheric pressure to 210°C. , usually 7-70 YuA-
at a pressure of 0.1 to 316°C and a temperature of 24 to 316°C.
It can be carried out for 24 hours, preferably 0.2 to 8 hours. In addition, in Table 1, the steps where the amount of monomer charged is 0 are as follows:
This means that the polymerization step was omitted.

In Table 1, Bd represents butadiene and St represents styrene.

Table 1 Example 1 350 parts of polyethylene M170, 50 parts of the copolymer of block polymer No. 1 in Table 1, and 2 parts of phenodeazine as an antioxidant were added to Nakatani Kikai Co., Ltd.
Using a disk twin-screw vent type extruder, melt mixing is performed at a temperature of 200° C., an extruder rotation speed of 60 rpm, and a discharge rate of 1k 4' at 9/hr to prepare a preliminary mixing composition. Then, PP1
68 parts, Styron QH40532 parts, 10 parts of the above premixing composition, and 0.65 parts of Mark A030 (manufactured by Ateca Arcus (a)) as a stabilizer were mixed in a pre-goo, using a twin-screw extruder, and the maximum cylinder temperature A pellet was obtained by extrusion at 290°C, and a test piece was prepared using an injection molding machine at 275°C and used for testing. The results are shown in Table 2.

It can be seen that the thermoplastic resin composition blended with the elastomer defined in the present invention has excellent impact resistance, stress crack resistance, and appearance of molded products.

Examples 2 to 3 Example 1 is exactly the same as Example 1, except that the copolymer of block polymer number 1 in Table 1 is replaced with the copolymer of block polymer number 2 and 3 of Table 1. Examples 2 and 3 were performed according to the procedure.

The results are shown in Table 2. It can be seen that a composition that met the object of the present invention was obtained.

Examples 4 to 7 In Example 1, polyethylene M-1703'? : Polyethylene M-6520, Polyethylene F-2270.
Example 4 was carried out in exactly the same manner as in Example 1 except for replacing polyethylene yLF-24088 and JSREPO7P.
~7 was performed. The results are shown in Table 2. It can be seen that a composition that meets the objectives of the present invention was obtained.

Example 8 In Example 1, polyethylene M1703 and the first
The crosstalk ratio with the copolymer of block polymer number 1 in the table is 7.
= 3 was tested using the same procedure as in Example 1. The results are shown in Table 2.

It can be seen that a composition that meets the objectives of the present invention was obtained.

Example 9 Tests were carried out in the same manner as in Example 1 except that 15 parts of the preliminary crosstalk composition was added in Example 1. The results are shown in Table 2. It can be seen that a composition that met the objective K was obtained.

Comparative Example 1 A test was conducted in exactly the same manner as in Example 1, except that the copolymer of block polymer number 1 in Table 1 was replaced with a non-hydrogenated copolymer. The results are shown in Table 2. Stress crack resistance is not good enough.

Comparative Example 2 In Example 1, the test was conducted in exactly the same manner as in Example 1, except that the copolymer with block polymer number 1 in Table 1 was replaced with the copolymer with block polymer number 1 in Table 1. provided. The results are shown in Table 2. Stress crack resistance is not good enough, and peeling is observed in the molded product.

Comparative Example 3 All of Example 1 (tested in the same procedure) except that the copolymer with block polymer number 1 in Table 1 was replaced with the copolymer with block polymer number 5 in Table 1. The results are shown in Table 2. The stress crack resistance was not sufficiently good, and peeling was observed in the molded product.

Comparative Example 4 In Example 1, the test was conducted in exactly the same manner as in Example 1, except that the copolymer of block polymer No. 1 in Table 1 was replaced with the copolymer of block polymer No. 6 in Table 1. provided. The results are shown in Table 2. Stress crack resistance is not good enough, and some peeling is observed in the molded product.

Comparative Example 5 In Example 1, polyethylene M1703
The crosstalk ratio with the copolymer of block polymer number 1 in the table is 8.
The test was conducted in exactly the same manner as in Example 5, except that =2. The results are shown in Table 2.

Stress crack resistance is not good enough, and some peeling is observed in the molded product.

Comparative Example 6 In Example 1, the crosstalk ratio of polyethylene M1703 and the copolymer of block polymer No. 1 in Table 1 was set to 2=8.
The test was carried out in exactly the same manner as in Example 1, except for the following. The results are shown in Table 2.

It can be seen that the stress crack resistance is not sufficiently good.

Comparative Example 7 Example 1 except that 310 parts of polyethylene M170 was added in place of the pre-blended mixture in Example 1.
I completed the exam using the exact same procedure. The results are shown in Table 2. It can be seen that the stress crack resistance is not good.

In addition, peeling of the thin layer is observed in the molded product.

Comparative Example 8 In Example 1, the pre-blended mixture KR was replaced with the first one.
The test was carried out in the same manner as in Example 1 except that 10 parts of the copolymer of block polymer No. 1 in the table was added. The results are shown in Table 2.

It can be seen that the impact resistance and stress crack resistance are not good. In addition, some peeling is observed in the molded product.

Comparative Example 9 In Example I, all procedures were carried out in the same manner as in Example 1, except that 5 parts of polyethylene M1703 and 5 parts of the copolymer of block polymer No. 1 in Table 1 were added instead of the pre-blended mixture. The test results are shown in Table 2. It can be seen that the impact resistance and stress crack resistance are not good.

In addition, peeling of the thin layer is observed in the molded product.

Examples 10-12. Comparative Example 10 Each component was blended in the parts shown in Table 3, and tested in the same manner as in Example 1. The results are shown in the table below.

It can be seen that the thermoplastic resin composition having the blending ratio specified in the present invention has excellent impact resistance and stress crack resistance while having heat resistance, which is a characteristic of polyphenylene ether-based materials. On the other hand, at a blending ratio that deviates from the present invention, the stiffness decreases,
It can be seen that the heat resistance deteriorates and the excellent properties originally possessed by polyphenylene ether materials are lost.

Table 3 [Effects of the Invention] The thermoplastic resin composition of the present invention has high impact resistance and stress crack resistance without deteriorating the excellent properties such as rigidity and heat resistance originally possessed by polyphenylene ether resin. It is a composition with improved properties, and is of great industrial significance as it has dramatically expanded the field of application of polyphenylene ether resins.

Patented wheat flour Asahi Kasei Industries, Ltd.

Claims (1)

[Scope of Claims] [1] A total of 100 parts by weight of (a) 20 to 80 parts by weight of polyphenylene ether resin, and (b) 80 to 20 parts by weight of styrene resin, (c) 30 to 30 parts by weight of polyolefin resin. 70 parts by weight and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ A pre-kneaded composition consisting of 70 to 30 parts by weight of a resinous block copolymer (n is an integer of 1 or 2, the content of component A is 50 to 65% by weight) Thermoplastic resin composition containing 20 parts by weight [2] The polyolefin polymer is polyethylene, polypropylene, polyisobutylene, a copolymer of ethylene and propylene, a copolymer of ethylene and an organic ester, or any of the above. The thermoplastic resin composition according to claim 1 selected from among the mixtures [3] ▲ Numerical formula, chemical formula, table, etc. ▼ The resinous block copolymer has a weight average molecular weight of 100,000 to The thermoplastic resin composition according to claim 1, which is a resinous copolymer of 600,000 [4] The polyphenylene ether resin is a poly(2,6-
The thermoplastic resin composition according to claim 1, which is dimethyl-1,4-phenylene) ether [5] The thermoplastic resin composition according to claim 1, wherein the styrenic resin is polystyrene. [6] The thermoplastic resin composition according to claim 1, wherein the styrenic resin is rubber-modified high-impact polystyrene.